2, 3-anthraquinone-dicarboximide dye developers



United States Patent 3,255,206 2,3-ANTHRAQUINONE-DICARBOXIMIDE DYE DEVELOPERS v Myron S. Simon, Newton Center, Mass., assignor to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware No Drawing. Filed Oct. 23, 1962, Ser. No. 232,585 4 Claims. (Cl. 260-326) This application is in part a continuation of copending application, Serial No. 678,439, filed August 15, 1957, and now abandoned. I

This invention relates to photography and more particularly to products, compositions and processes for the development of photosensitive silver halide elements.

It is one object of the present invention to provide novel processes and compositions for the development of silver halide emulsions, in which novel colored developing agents are used.

Another object is to provide novel processes and compositions for the development of silver halide emulsions, in which the novel developing agent is capable of developing an exposed silver halide emulsion and imparting a reversed or positive colored image of the developed image to a superposed image-receiving material.

A further object is to provide novel silver halide developing agents and novel products, processes and compositions suitable for use in preparing monochromatic and multichromatic photographic images.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products and compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

The objects of this invention may be accomplished by the use of certain novel dyes which have the ability to develop images present in an exposed silver halide emulsion; thus they may be referred to as dye developers.

Howard G. Rogers, discloses diffusion transfer processes wherein a photographic negative material, such as a photographic element comprising an exposed silver halide emulsion, is developed in the presence of a dye developer to impart to an image-receiving layer a reversed or positive dye image of the developed image by permeating into said emulsion a suitable liquid processing composition and bringing said emulsion into superposed relationship with an appropriate image-receiving layer. The inventive concepts herein set forth provide novel dye developers for use in such processes.

In carrying out the process of this invention, a photosensitive element containing a silver halide emulsion is exposed and wetted with a liquid processing composition, for example by immersing, coating, spraying, flowing, etc., in the dark, and the photosensitive element superposed prior to, during or after wetting, on an imagereceiving element. In a preferred embodiment, the photosensitive element contains a layer of dye developer, and the liquid processing composition is applied to the photosensitive element in a uniform layer as the photosensitive element is brought into superposed position with an image-receiving element. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently due, at least in part, to a change in the solubility characteristics of the dye developer upon oxidation, and especially as regards its solubility in alkaline solutions. It may also be due, in part, to a tanning elfect on the emulsion by the oxidized developing agent. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer. The image-receiving layer receives a depthwise diffusion, from the emulsion, of unoxidized dye developer, without aprevealed by stripping the image-receiving layer from the silver halide emulsion at the end of the imbibition period.

The dye developers of this invention may be utilized in the photosensitive element, for example in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition. In a preferred embodiment, a coating or layer of the' dye developer is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving layer when in superposed relationship therewith. Placing the dye developer behind the emulsion layer, as in the'preferred embodiment, has the advantage of providing increased contrast in the positive image, and also minimizes any lightfiltering action by the colored dye developer. In this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing about 0.5 to 8%, by weight, of the dye developer. centrations may be used if the dye developer is utilized as a component of the liquid processing composition. In an especially useful mode of disposing the dye developers in the photosensitive elements, the dye developer is dissolved in a water-immiscible solvent and then dispersed in a gelatin coating solution.

The liquid processing composition which is used in the processes herein disclosed comprises at least an aqueous Similar con- 4 solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. In some instances, it may contain an additional silver halide developing agent. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosityincreasing compound constituting film-forming material of the type which, when spread over a water-absorbent base, will form a relatively firm and relatively stable film. A preferred film-forming material is a high. molecular weight polymer such as a polymeric, water-soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxylmethyl cellulose. Other film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected when left in solution for a long period of time may also be used.

The novel dye developers of this invention are amino or hydroxy-substituted anthraquinone dyes having bonded directly to the 2, 3 carbon atoms of the anthraquinone nucleus, a substituent of the formula:

wherein: Y is a dihydroxyphenyl silver halide developing radical, e.g., p-dihydroxyphenyl, o-dihydroxyphenyl and halogen and alkyl substituted derivatives thereof; X is a divalent radical or a covalent bond; and each of R and R may be hydrogen or a lower alkyl radical; said substituent being bonded to said nuclear carbon atoms through said II C..

radicals, e.g., one of said radicals is bonded directly to the nuclear carbon atom of the 2 position, the other of said radicals to the 3 position carbon atom of the anthraquinone nucleus. As used herein, the term amino or hydroxy-substituted'anthraquinone dyes connotes anthraquinone dyes having at least one amino and/or hydroxy substituent substituted on the anthraquinone nucleus in a positionother than the 2 or 3 position.

In a preferred embodiment, X is a lower alkylene radical, e.g., methylene, ethylene, propylene, etc., in which case, said substituent may be represented by the follow ing formula:

YX1N/ wherein: Y has the meaning heretofore noted and X is a lower alkylene radical.

In addition to containing an amino and/or hydroxy radical and the substituent of Formulae A or B, it is con- (C) z o OH 0 H XIN U C n Y I z 0 OH wherein X is a lower alkylene radical, and each Z is hydroxy or amino and may be the same or different.

As an example of a dye developer within the class comprising the preferred embodiment of the invention, mention may be made of:

lyi-(liaminoN- 5'2 ,5 -dlhydr0xyphenyl-a-rnethyl-ethyl) 2,3-nnthraquinone dicarboximide As an example of another dye developer within the scope of this invention, mention may be made of the following:

i i on 3 GHHiaN 0 I OH on l-amino--hydroxy-N-(5-2,5'-dihydroxyphenyl-a-methylethyl) -2,3-an thraquinone-dicarboxylmide The novel dye developers of this invention may be prepared by reacting a 2,3-anthraquinone-dicarboxi-mide dye and an amino-substituted dihydroxyphenyl compound, or an acid salt of such amino compound, in the presence of an equivalent of caustic under conditions of elevated temperature.

As examples of suitable amino substituted dihydroxyphenyl compounds, mention may be made of compounds within the formula:

etc., arylene radicals, such as p-phenylene, alkarylene radicals, such as and acyl radicals, such as 5. It is to be understood that the expressions alkylene," arylene and alkarylene include substituted derivatives thereof, i.e., they may be further substituted by suitable alkyl radicals, such as methyl, ethyl, etc., aryl radicals, such as a phenyl radical, or acyl radicals, such as an acetyl radical.

The preferred compound within the group represented by Formula D is:

C 2CI3H-CHs NH,

2- (B-amindpropyl) -hydroqulnone B-Aminoethyl-hydroquinone and B-amino-B-ethyl-ethyl hydroquinone may also be used in the preferred embodiment.

As previously mentioned, Where desirable divalent inorganic radicals may be employed, either alone or as constituent components of divalent, organic radicals, in the practice of this invention. Among the preferred compounds utilizing a divalent inorganic radical as a constituent component of a divalent oragnic radical, mention may be made of compounds within the formula:

wherein V is an oxy, sulfonyl or thio radical; U is the number of carbon atoms necessary to constitute the desired aliphatic or aromatic configuration; and Y has the same meaning as above.

As an example of a suitable compound within the group represented by Formula F, mention may be made of:

(a) on S-C Pia-C Hz-NHz I OH B-Amlno-ethyl-thio-hydroqninone The preparation of 2,3-anthraquinone-dicarboximide dyes suitable for use in the practice of this invention is disclosed in US. Patent No. 2,628,963, issued February 17, 1953, to Laucius and Speck and U8. Patent No. 2,701,802, issued February 8, 1955, to Boyd.

The following example illustrates the preparation of dye developers within the scope of this invention and is given for purposes of illustration only.

Example 1 1,4-diamino-2,3 anthraquinone dicarboximide (0.005 mol) and 2-(B-amino'propyl)-hydroquinone (0.013 mol) is dissolved with stirring in methyl Cellosolve. A sodium hydroxide solution (0.013 mol) is added to the mixture in an atmosphere of nitrogen. The resultant mixture is heated at approximately 100 C. for 9.5 hours in an atmosphere of nitrogen. The mixture is then cooled and acidified dropwise with glacial acetic acid. The resultant greenish-blue precipitate is removed from the mixture by filtration, washed with methanol and then washed with water. The precipitate is purified by recrystallization from a methyl cellosolve/water mixture. The resultant 1,4-diamino-N-(,B-2,5'-dihydroxyphenyl-a methyl-ethyl)-2,3-anthraquinone-dicarboximide [Formula 1], a greenish-blue compound, is soluble in sodium hydroxide, reduces silver halide and melts at 274 to 277 C.

The absorption spectrum of the compound exhibits a 7\,,,,,,; at 674 mo in pyridine, a: 15,800.

Elemental analysis of the product as C H O -H 0:

0, percent H, percent N, percent Found Calculated Example 2 A photosensitive'element is prepared by coating a gelatin-coated film base with a solution containing 3% of 1,4-diamino-N-( 13-215 dihydroxyphenyl a methyl! ethyl)-2,3-anthraquinone-dicarboximide [Formula 1 as prepared in Example 1], in a 4% solution of cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetra-hydrofuran. After this coating has dried, a silver iodobromide emulsion is applied. This photosensitive element is exposed and processed by sperading an aqueous liquid processing composition comprising:

Percent Sodium carboxymethyl cellulose 4.0 1-phenyl-3-pyrazolidone 0.2 Sodium hydroxide 2.0 Potassium bromide 0.2

between said photosensitive element and an image-receiving element as said elements are brought into superposed relationship. The image-receiving element comprises a cellulose acetate-coated baryta paper which has been coated with a solution comprising 10% Nylon Type F8 (trade name of E. I. du Pont de Nemours & Co., Wilmington, Delaware, for N-methoxymethyl polyhexamethylene adipamide) in aqueous isopropanol. After an imbibition period of approximately one minute, the image-receiving element is separated and contains a cyan positive dye image of the photographed subject.

As was mentioned previously, the compounds of this invention are particularly useful in photographic products, processes and compositions such as are described and claimed in US. Patent No. 2,983,606. This is quite surprising, since prior to the present invention it was not believed that compounds containing four linearly fused rings would be able to diffuse between-the pores of the gelatin or equivalent colloidal material of the emulsion within ashort, reasonable time to form a transfer image of satisfactory density. Stated another way, as far as is known, it was never obvious heretofore that the compounds of the present invention could be utilized to form color images by diffusion transfer, since it was believed that a molecule having four linearly fused rings would be unable to diffuse to the image-receiving element.

The dye developers of this invention are also useful in integral multilayer photosensitive elements for use in silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements of this invention are especially useful in composite roll film intended for use in a Polaroid Land Camera, sold by Polaroid Corporation, Cambridge 39, Massachusetts, or a similar camera structure such, for example, as the camera forming the subject matter of U.S. Patent No. 2,435,717, issued to Edward H. Land on February 10, 1948. In general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element may be superposed on the imagereceiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well known to the art. See, for example, U.S. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-rnethylaminophenol (Metol); 2,4-dia-minophenol (Amidol); benzylaminophenol; hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydroquinone, or 4'methylphenylhydroquinone; or a 3-pyrazolidone such as l-phenyl-3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in the copending application of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960, now U.S. Patent No. 3,173,786.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films,

plates or papers to obtain black-and-white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may comprise an aqueous solution of approximately 1-2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-sufficient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called auto-coupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of imagereceiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in U.S. Patent No. 2,647,049 to Edwin E. Land.

As examples of useful,image-receiving materials, mention may be made of nylon, e.g., N-methoxymethyl-polyhexamethylene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine. The image-receiving element also may contain a development restrainer, e.g., 1phenyl-S-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August 22, 1960.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in U.S. Patent No. 2,968,554, issued to Edwin H. Land on January 17, 1961.

.The novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon.

In the preceding portions of the specification, the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.

Copending U.S. application, Serial No. 232,584, filed concurrently herewith, and now U.S. Patent No. 3,131,- 061, claims the photographic utilization of the novel compounds of the present invention.

Since certain changes may be made in the above products without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. An anthraquinone dye having a member of the group consisting of NH and OH on each of the 1 and 4 carbon atoms of the anthraquinone nucleus, each of the 2 and 3 carbon atoms of said nucleus being bonded directly to one of the free valences of the radical:

3. 1,4 diamino N (B 2,5'-dihydroxyphenyl-a-methyl-ethyl)-2,3-anthraquinone-dicarboximide.

, 9 4. 1-amino-#hydroxy-N-(fi-ZQS dihydroxypheny-l ocmethyl-ethyl) -2,3 -anthraquinone-dicarboximide.

References Cited by the Examiner UNITED STATES PATENTS 2,604,399 7/1952 Donovan e t a1 260326 2,628,963 2/1953 Laucius et a1. 260326 3,076,808 2/1963 Blout et a1. 260278 1 0 OTHER REFERENCES Bergman: The Chemistry of Acetylene and Related Compounds, page 80 (1948).

5 HENRY R. JILES, Acting Primary Examiner.

EGON E. BERG, Examiner.

MARY U. OBRIEN, Assistant Examiner. 

1. AN ANTHRAQUINONE DYE HAVING A MEMBER OF THE GROUP CONSISTING OF NH2 AND -OH ON EACH OF THE 1 AND 4 CARBON ATOMS OF THE ANTHRAQUINONE NUCLEUS, EACH OF THE 2 TO 3 CARBON ATOMS OF SAID NUCLEUS BEING BONDED DIRECTLY TO ONE OF THE FREE VALENCES OF THE RADICAL: 